Novel process

Abstract

A novel process for the preparation of pent-4-enoic acids of the formula ##STR1## wherein X is selected from the group consisting of hydrogen, cyano and alkoxycarbonyl of 2 to 5 carbon atoms and Y is selected from the group consisting of hydrogen, cyano, alkoxycarbonyl 2 to 5 carbon atoms, acyl of an organic carboxylic acid of 2 to 7 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms and arylsulfonyl of 6 to 7 carbon atoms with the proviso that X and Y are not both hydrogen comprising reacting a compound of the formula ##STR2## wherein R is selected from the group consisting of acyloxy of an organic carboxylic acid of 1 to 7 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms and arylsulfonyl of 6 to 7 carbon atoms with an anion derivative of a compound of the formula ##STR3## wherein X 1 and Y 1 have the above definition for X and Y, respectively, except hydrogen in the presence of a palladium compound or nickel (o) complex and optionally a catalytic quantity of a ligand to obtain a compound of the formula ##STR4## wherein X 1 and Y 1 have the above definition and optionally subjecting the latter to a decarbalkoxylation when X 1 or Y 1 is alkoxycarbonyl or to a reduction when X 1 is arylsulfonyl to obtain the corresponding compound of formula I.

What we claim is: 
     
       1. A process for the preparation of pent-4-enoic acids of the formula ##STR21## wherein X 1  is selected from the group consisting of cyano and alkoxycarbonyl of 2 to 5 carbon atoms and Y 1  is selected from the group consisting of cyano, alkoxycarbonyl of 2 to 5 carbon atoms, acyl of an organic carboxylic acid of 2 to 7 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms and carbocyclic arylsulfonyl of 6 to 7 carbon atoms comprising reacting in the liquid phase a compound of the formula ##STR22## wherein R is selected from the group consisting of acyloxy of an organic carboxylic acid of 1 to 7 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms and carbocyclic arylsulfonyl of 6 to 7 carbon atoms with an alkali metal anion derivative of a compound of the formula ##STR23## wherein X 1  and Y 1  have the above definition in the presence of a palladium complex or nickel (o) complex and optionally a catalytic quantity of a ligand to obtain a compound of the formula ##STR24## wherein X 1  and Y 1  have the above definition. 
     
     
       2. The process of claim 1 wherein Y 1  is alkoxycarbonyl of 2 to 5 carbon atoms or --CN. 
     
     
       3. The process of claim 1 wherein X 1  is --CN. 
     
     
       4. The process of claim 1 wherein a palladium (II) complex is used. 
     
     
       5. The process of claim 4 wherein the complex is bis(η 3  -allyl)-di-μ-chloro-dipalladium (II). 
     
     
       6. The process of claim 1 wherein a palladium (o) complex is used. 
     
     
       7. The process of claim 6 wherein the complex is tetrakis-(triphenylphosphine)-palladium. 
     
     
       8. The process of claim 6 wherein the complex is di-(1,2-bis-diphenylphosphine-ethane)-palladium. 
     
     
       9. The process of claim 1 wherein a nickel (o) complex is used. 
     
     
       10. The process of claim 9 wherein the complex is formed in situ by reduction of a nickel (II) complex. 
     
     
       11. The process of claim 10 wherein the complex is formed by reaction of nickel dichloride with a compound selected from the group consisting of triphenyl phosphine, tributyl phosphine, triisopropyl phosphine, diphenyl phosphino-ethane, diphenylphosphino propane, diphenyl-phosphino-butane and diphenyl phosphinohexane. 
     
     
       12. The process of claim 1 wherein the ligand is selected from the group consisting of triphenyl phosphine, diphenyl phosphinoethane, hexamethyl phosphotriamide, triethyl phosphite and triphenyl phosphite, hydroquinone. 
     
     
       13. The further process of claim 1 wherein one of X 1  or Y 1  is alkoxycarbonyl and the compound of formula I is subjected to a decarbalkoxylation. 
     
     
       14. The further process of claim 1 wherein Y 1  is arylsulfonyl and the compound of formula I is subjected to reaction with a reducing agent to obtain a compound wherein Y 1  is hydrogen. 
     
     
       15. The process of claim 10 wherein the reducing agent is magnesium isopropyl chloride.